Graphene derivatives and electrocatalysts as composite electrodes for selective detection of catecholamine neurotransmitters
- Authors: Luhana, Charles Benjamin
- Date: 2024-04-05
- Subjects: Uncatalogued
- Language: English
- Type: Academic theses , Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/435907 , vital:73211 , DOI 10.21504/10962/435907
- Description: In this thesis, we investigated the development of electrochemical sensing electrodes based on graphene derivatives and the electrocatalyst composites of metallophthalocyanines and metal oxides towards the selective and sensitive detection of catecholamine neurotransmitters (NTs). The graphene and its derivatives offer excellent electron conductivity and hence their use as base electrode materials. Metallophthalocyanines are N4-macrocyclic metal organic complexes that have structural modification flexible and 18-π electrons with excellent electrocatalytic properties. They can incorporate transition metal ions at the centre of the macrocycle ring, and this further enhances their electrocatalytic activity. Transition metal oxides are of interest as these also offer excellent redox properties and pH sensitivity. A pH sensitive electrochemical sensor based on aminated graphene quantum dots (AmGQDs) and cobalt tetra carboxyphenoxy phthalocyanine (CoTCPhOPc) covalent conjugates onto the pre-grafted isophthalic acid (IPA) gold electrode was fabricated. It displayed excellent analytical performance towards the detection of dopamine (DA), norepinephrine (NOR) and epinephrine (EP). The electrochemical sensor exhibited good ability to suppress the background current due to ascorbic acid (AA), a major interference in the detection catecholamine NTs. The carboxylic acid functional group of cobalt phthalocyanine induced the pH sensitivity of the thin film and electrostatic repulsion of the negatively charged ascorbate (AA-) anion at physiological pH. In addition, the electrode could screen-off biological molecules in the newborn calf serum as a representative of a real sample. An electrochemically reduced graphene oxide–based cobalt phthalocyanine polymer (polyCoTAPc) composite electrochemical sensor was fabricated on glassy carbon electrode, GCE-ERGO/polyCoTAPc. The GCE-ERGO/polyCoTAPc could detect dopamine and paracetamol simultaneously as co-existing analytes in buffer and synthetic urine samples. We observed, (i) very strong absorption of the materials, (ii) increase in the electrode surface area, (iii) excellent conductivity, and (iv) electrocatalytic activity of the ERGO/polyCoTAPc composite surface. Furthermore, a simple ultrasensitive electrochemical sensor based on nickel hydroxide thin film electrodeposited onto reduced graphene oxide-molybdenum disulfide (RGO/MoS2) composite resulted in the electrochemical sensor that can selectively and simultaneously detect ascorbic acid, dopamine, and uric acid. A distinct peak potential separation was observed with excellent electrocatalytic oxidation currents. The electrochemical sensors developed in this work exhibited high sensitivity, selectivity, stability, and low detection limits suitable for the detection and determination of catecholamine NTs. , Thesis (PhD) -- Faculty of Science, Chemistry, 2024
- Full Text:
- Date Issued: 2024-04-05
- Authors: Luhana, Charles Benjamin
- Date: 2024-04-05
- Subjects: Uncatalogued
- Language: English
- Type: Academic theses , Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/435907 , vital:73211 , DOI 10.21504/10962/435907
- Description: In this thesis, we investigated the development of electrochemical sensing electrodes based on graphene derivatives and the electrocatalyst composites of metallophthalocyanines and metal oxides towards the selective and sensitive detection of catecholamine neurotransmitters (NTs). The graphene and its derivatives offer excellent electron conductivity and hence their use as base electrode materials. Metallophthalocyanines are N4-macrocyclic metal organic complexes that have structural modification flexible and 18-π electrons with excellent electrocatalytic properties. They can incorporate transition metal ions at the centre of the macrocycle ring, and this further enhances their electrocatalytic activity. Transition metal oxides are of interest as these also offer excellent redox properties and pH sensitivity. A pH sensitive electrochemical sensor based on aminated graphene quantum dots (AmGQDs) and cobalt tetra carboxyphenoxy phthalocyanine (CoTCPhOPc) covalent conjugates onto the pre-grafted isophthalic acid (IPA) gold electrode was fabricated. It displayed excellent analytical performance towards the detection of dopamine (DA), norepinephrine (NOR) and epinephrine (EP). The electrochemical sensor exhibited good ability to suppress the background current due to ascorbic acid (AA), a major interference in the detection catecholamine NTs. The carboxylic acid functional group of cobalt phthalocyanine induced the pH sensitivity of the thin film and electrostatic repulsion of the negatively charged ascorbate (AA-) anion at physiological pH. In addition, the electrode could screen-off biological molecules in the newborn calf serum as a representative of a real sample. An electrochemically reduced graphene oxide–based cobalt phthalocyanine polymer (polyCoTAPc) composite electrochemical sensor was fabricated on glassy carbon electrode, GCE-ERGO/polyCoTAPc. The GCE-ERGO/polyCoTAPc could detect dopamine and paracetamol simultaneously as co-existing analytes in buffer and synthetic urine samples. We observed, (i) very strong absorption of the materials, (ii) increase in the electrode surface area, (iii) excellent conductivity, and (iv) electrocatalytic activity of the ERGO/polyCoTAPc composite surface. Furthermore, a simple ultrasensitive electrochemical sensor based on nickel hydroxide thin film electrodeposited onto reduced graphene oxide-molybdenum disulfide (RGO/MoS2) composite resulted in the electrochemical sensor that can selectively and simultaneously detect ascorbic acid, dopamine, and uric acid. A distinct peak potential separation was observed with excellent electrocatalytic oxidation currents. The electrochemical sensors developed in this work exhibited high sensitivity, selectivity, stability, and low detection limits suitable for the detection and determination of catecholamine NTs. , Thesis (PhD) -- Faculty of Science, Chemistry, 2024
- Full Text:
- Date Issued: 2024-04-05
The enemy release hypothesis and beyond: Lagarosiphon major invasion dynamics and management options for New Zealand using native natural enemies from South Africa
- Authors: Baso, Nompumelelo Catherine
- Date: 2024-04-05
- Subjects: Uncatalogued
- Language: English
- Type: Academic theses , Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/435627 , vital:73174 , DOI 10.21504/10962/435627
- Description: Numerous scientific investigations have demonstrated the destructive impact that exotic species can have on ecosystem services beyond a specific threshold. There are many explanations for why introduced plants are likely to be more successful outside their native range. One such explanation is offered by the Enemy Release Hypothesis (ERH), which states that plants automatically become superior competitors outside of their natural range due to release from top-down stressors (herbivory, parasites, and diseases) that is evident in the absence of their natural enemies. The underlying assumption of the ERH is that natural enemies are important regulators of plant species populations, and that the pressures from these natural enemies are felt more readily by native species compared to alien plants. Consequently, in the absence of such pressures, the ERH assumes that exotic plants can allocate more resources towards growth and reproduction, while effectively maintaining accumulated biomass. Classical biological control has previously been cited as evidence for the enemy release hypothesis. Therefore, the overarching aim and theme of this thesis was to investigate the role of ERH on the invasiveness of Lagarosiphon major (Ridl.) Moss ex Wager (Hydrocharitaceae) in New Zealand. Firstly, a literature search and a meta-analysis was used to synthesize existing studies in order to test for general applicability of this hypothesis to aquatic plant invasions. Furthermore, an empirical investigation was conducted in order to directly quantify enemy release in L. major populations invaded areas of New Zealand. To achieve this, various plant parameters of this plant, overall macrophyte and invertebrate diversity were measured and compared between sites in the native range in South Africa and the invaded areas in New Zealand. Although the meta-analysis showed variable evidence for this hypothesis depending on various modulating factors such as study type, plant growth form and measured parameters, for L. major, there was strong evidence of enemy release. The biogeographical comparisons showed that L. major exhibited increased fitness in most of the invaded sites, marked by elevated biomass accumulation, significantly higher shoot production, and the displacement of native plant species. The observed fitness advantages were directly correlated to a decrease in herbivory diversity and pressure upon the plant's introduction to New Zealand. Unlike the native populations, which contend with the presence of at least four co-occurring herbivores, including specialist herbivores, the invaded range had a substantially lower herbivore diversity, with only Hygraula nitens Butler (Lepidoptera: Crambidae) syn. Nymphula nitens, significantly damaging L. major. These findings emphasize the importance of understanding invasion ecology and theories such as ERH in order to advance aquatic plant management and also present valuable insights for developing effective strategies to mitigate the impact of invasive alien species on aquatic ecosystems. Specifically, results from the empirical investigation provide evidence in support of the ERH and highlight the suitability of implementing biological control strategies to manage the L. major invasion in New Zealand. Previous studies have shown the suitability of two specialist herbivores, Hydrellia lagarosiphon Deeming (Diptera: Ephydridae), and Polypedilum tuburcinatum Andersen (Diptera: Chironomidae), as potential biological control agents. This control strategy presents a sustainable and ecologically responsible approach, promoting coexistence between exotic plants and native species rather than displacement through competitive exclusion. With the apparent dominance of L. major at various New Zealand localities, the subsequent objective of this thesis was to investigate the competitive interactions between L. major and another invasive Hydrocharitaceae, Egeria densa Planchon, as driven by herbivory. Combinations of two host specific Ephydrid flies, H. lagarosiphon and H. egeriae, were used at eight different factorial combination of planting densities. The analysis of plant parameters and the application of inverse linear models revealed that L. major often exhibits relatively higher fitness, especially in low monoculture treatments when the two insects were isolated. However, multiple inverse linear models revealed that actual competitive outcomes are dependent on factors such as initial plant density and herbivory regime, with competitive interactions generally being mild. Nevertheless, the presence of H. lagarosiphon resulted in facilitation of E. densa growth. Thus, even at lower densities, these insects still had an impact on the observed interactions, further emphasizing suitability as damaging biological control agents. Lastly, focusing on the abiotic component of L. major invasion, Species Distribution Models (SDMs) were employed to map potential suitable habitat for this species, as well as predict the consequences of climate change on this. Correlative and mechanistic modelling was also used to simulate suitable habitat for potential biological control agents, thus addressing the potential for mismatches between host plant distribution and insect suitable range. The Maximum Entropy Species Distribution Modelling (MaxEnt) algorithm revealed that more than 90% of all freshwater ecosystems in New Zealand are susceptible to L. major invasion, with suitability projected to expand further under future climate scenarios. Moreover, correlative modelling using this method suggests limited suitable habitat for both herbivores. However, degree-day modelling, which also takes into account the physiological requirements, showed that H. lagarosiphon has the potential to produce viable populations in several parts of New Zealand. Overall, this thesis explored the intricate web of biotic and abiotic factors influencing the success of L. major outside its native range. The results emphasize the potential impacts of climate change on the invasion potential and management strategies for L. major. The findings also advocate for the implementation of sustainable and ecologically sound management solutions, such as biological control, to manage this species. , Thesis (PhD) -- Faculty of Science, Botany, 2024
- Full Text:
- Date Issued: 2024-04-05
- Authors: Baso, Nompumelelo Catherine
- Date: 2024-04-05
- Subjects: Uncatalogued
- Language: English
- Type: Academic theses , Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/435627 , vital:73174 , DOI 10.21504/10962/435627
- Description: Numerous scientific investigations have demonstrated the destructive impact that exotic species can have on ecosystem services beyond a specific threshold. There are many explanations for why introduced plants are likely to be more successful outside their native range. One such explanation is offered by the Enemy Release Hypothesis (ERH), which states that plants automatically become superior competitors outside of their natural range due to release from top-down stressors (herbivory, parasites, and diseases) that is evident in the absence of their natural enemies. The underlying assumption of the ERH is that natural enemies are important regulators of plant species populations, and that the pressures from these natural enemies are felt more readily by native species compared to alien plants. Consequently, in the absence of such pressures, the ERH assumes that exotic plants can allocate more resources towards growth and reproduction, while effectively maintaining accumulated biomass. Classical biological control has previously been cited as evidence for the enemy release hypothesis. Therefore, the overarching aim and theme of this thesis was to investigate the role of ERH on the invasiveness of Lagarosiphon major (Ridl.) Moss ex Wager (Hydrocharitaceae) in New Zealand. Firstly, a literature search and a meta-analysis was used to synthesize existing studies in order to test for general applicability of this hypothesis to aquatic plant invasions. Furthermore, an empirical investigation was conducted in order to directly quantify enemy release in L. major populations invaded areas of New Zealand. To achieve this, various plant parameters of this plant, overall macrophyte and invertebrate diversity were measured and compared between sites in the native range in South Africa and the invaded areas in New Zealand. Although the meta-analysis showed variable evidence for this hypothesis depending on various modulating factors such as study type, plant growth form and measured parameters, for L. major, there was strong evidence of enemy release. The biogeographical comparisons showed that L. major exhibited increased fitness in most of the invaded sites, marked by elevated biomass accumulation, significantly higher shoot production, and the displacement of native plant species. The observed fitness advantages were directly correlated to a decrease in herbivory diversity and pressure upon the plant's introduction to New Zealand. Unlike the native populations, which contend with the presence of at least four co-occurring herbivores, including specialist herbivores, the invaded range had a substantially lower herbivore diversity, with only Hygraula nitens Butler (Lepidoptera: Crambidae) syn. Nymphula nitens, significantly damaging L. major. These findings emphasize the importance of understanding invasion ecology and theories such as ERH in order to advance aquatic plant management and also present valuable insights for developing effective strategies to mitigate the impact of invasive alien species on aquatic ecosystems. Specifically, results from the empirical investigation provide evidence in support of the ERH and highlight the suitability of implementing biological control strategies to manage the L. major invasion in New Zealand. Previous studies have shown the suitability of two specialist herbivores, Hydrellia lagarosiphon Deeming (Diptera: Ephydridae), and Polypedilum tuburcinatum Andersen (Diptera: Chironomidae), as potential biological control agents. This control strategy presents a sustainable and ecologically responsible approach, promoting coexistence between exotic plants and native species rather than displacement through competitive exclusion. With the apparent dominance of L. major at various New Zealand localities, the subsequent objective of this thesis was to investigate the competitive interactions between L. major and another invasive Hydrocharitaceae, Egeria densa Planchon, as driven by herbivory. Combinations of two host specific Ephydrid flies, H. lagarosiphon and H. egeriae, were used at eight different factorial combination of planting densities. The analysis of plant parameters and the application of inverse linear models revealed that L. major often exhibits relatively higher fitness, especially in low monoculture treatments when the two insects were isolated. However, multiple inverse linear models revealed that actual competitive outcomes are dependent on factors such as initial plant density and herbivory regime, with competitive interactions generally being mild. Nevertheless, the presence of H. lagarosiphon resulted in facilitation of E. densa growth. Thus, even at lower densities, these insects still had an impact on the observed interactions, further emphasizing suitability as damaging biological control agents. Lastly, focusing on the abiotic component of L. major invasion, Species Distribution Models (SDMs) were employed to map potential suitable habitat for this species, as well as predict the consequences of climate change on this. Correlative and mechanistic modelling was also used to simulate suitable habitat for potential biological control agents, thus addressing the potential for mismatches between host plant distribution and insect suitable range. The Maximum Entropy Species Distribution Modelling (MaxEnt) algorithm revealed that more than 90% of all freshwater ecosystems in New Zealand are susceptible to L. major invasion, with suitability projected to expand further under future climate scenarios. Moreover, correlative modelling using this method suggests limited suitable habitat for both herbivores. However, degree-day modelling, which also takes into account the physiological requirements, showed that H. lagarosiphon has the potential to produce viable populations in several parts of New Zealand. Overall, this thesis explored the intricate web of biotic and abiotic factors influencing the success of L. major outside its native range. The results emphasize the potential impacts of climate change on the invasion potential and management strategies for L. major. The findings also advocate for the implementation of sustainable and ecologically sound management solutions, such as biological control, to manage this species. , Thesis (PhD) -- Faculty of Science, Botany, 2024
- Full Text:
- Date Issued: 2024-04-05
The Zimbabwe National Gender Policy (NGP) 2013–2017 and Women’s Economic Empowerment (WEE): a study of small-scale gold miners in the Bubi and Gwanda rural districts, Zimbabwe
- Moyo, Phoebe Michelle Zibusiso Sandi
- Authors: Moyo, Phoebe Michelle Zibusiso Sandi
- Date: 2024-04-03
- Subjects: Uncatalogued
- Language: English
- Type: Academic theses , Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/434638 , vital:73092 , DOI 10.21504/10962/434638
- Description: The study examines the impact of Zimbabwe’s second National Gender Policy (NGP) 2013-2017 under the Ministry of Women’s Affairs, Gender and Community Development on women’s access to and control over productive resources in the artisanal and small-scale gold mining sector in Bubi and Gwanda rural districts of Zimbabwe. Despite the implementation of the NGP over the past fourteen years, its effect on the economic empowerment of women has not been investigated adequately. Women’s economic empowerment (WEE) is recognized as a crucial development strategy. However, it faces challenges related to the tensions between structure and agency. Some perceive WEE as an entrepreneurial concept focusing on equal access and control over productive resources like credit, equipment, skills, and business training. Others argue that WEE should encompass more than just resource access and control by addressing structural factors that hinder women’s agency e.g. unequal social relations between men and women, patriarchy, unpaid care work, and sociocultural norms. The study employed a hybrid lens, combining structure and agency to analyse the implementation of the NGP’s empowerment programs. Drawing on Kabeer’s (1994) Social Relations Approach (SRA), the study utilized two key concepts from the SRA, namely social relations and institutional analysis, to examine the interaction between the NGP and various institutions (market, community, and family) where women are located. To gain a comprehensive understanding of the ways in which the NGP has supported or impeded WEE among the female small-scale gold miners in Bubi and Gwanda, a qualitative approach was employed as an investigative method. The findings indicated that the NGP adopts a liberal or agency centred approach to WEE. This approach emphasizes women’s agency and their ability to fulfil their potential in the public sphere. The NGP has facilitated access to credit, equipment, skills, and business training. However, the evidence also highlighted the uneven implementation of the NGP’s empowerment programs between the Bubi and Gwanda districts. Overall, the evidence revealed that, while the NGP has addressed gender inequalities to a limited degree, it has also reinforced class inequalities. The NGP’s empowerment programs have overlooked the structural factors that keep women in subordinate positions, such as the unequal social relations that exist between men and women, patriarchy, unpaid care work and sociocultural norms. , Thesis (PhD) -- Faculty of Humanities, Sociology, 2024
- Full Text:
- Date Issued: 2024-04-03
- Authors: Moyo, Phoebe Michelle Zibusiso Sandi
- Date: 2024-04-03
- Subjects: Uncatalogued
- Language: English
- Type: Academic theses , Doctoral theses , text
- Identifier: http://hdl.handle.net/10962/434638 , vital:73092 , DOI 10.21504/10962/434638
- Description: The study examines the impact of Zimbabwe’s second National Gender Policy (NGP) 2013-2017 under the Ministry of Women’s Affairs, Gender and Community Development on women’s access to and control over productive resources in the artisanal and small-scale gold mining sector in Bubi and Gwanda rural districts of Zimbabwe. Despite the implementation of the NGP over the past fourteen years, its effect on the economic empowerment of women has not been investigated adequately. Women’s economic empowerment (WEE) is recognized as a crucial development strategy. However, it faces challenges related to the tensions between structure and agency. Some perceive WEE as an entrepreneurial concept focusing on equal access and control over productive resources like credit, equipment, skills, and business training. Others argue that WEE should encompass more than just resource access and control by addressing structural factors that hinder women’s agency e.g. unequal social relations between men and women, patriarchy, unpaid care work, and sociocultural norms. The study employed a hybrid lens, combining structure and agency to analyse the implementation of the NGP’s empowerment programs. Drawing on Kabeer’s (1994) Social Relations Approach (SRA), the study utilized two key concepts from the SRA, namely social relations and institutional analysis, to examine the interaction between the NGP and various institutions (market, community, and family) where women are located. To gain a comprehensive understanding of the ways in which the NGP has supported or impeded WEE among the female small-scale gold miners in Bubi and Gwanda, a qualitative approach was employed as an investigative method. The findings indicated that the NGP adopts a liberal or agency centred approach to WEE. This approach emphasizes women’s agency and their ability to fulfil their potential in the public sphere. The NGP has facilitated access to credit, equipment, skills, and business training. However, the evidence also highlighted the uneven implementation of the NGP’s empowerment programs between the Bubi and Gwanda districts. Overall, the evidence revealed that, while the NGP has addressed gender inequalities to a limited degree, it has also reinforced class inequalities. The NGP’s empowerment programs have overlooked the structural factors that keep women in subordinate positions, such as the unequal social relations that exist between men and women, patriarchy, unpaid care work and sociocultural norms. , Thesis (PhD) -- Faculty of Humanities, Sociology, 2024
- Full Text:
- Date Issued: 2024-04-03
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